CN110550615B - Preparation method of high-energy-density lithium iron phosphate - Google Patents
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- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 80
- 239000000243 solution Substances 0.000 claims abstract description 80
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 70
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000004254 Ammonium phosphate Substances 0.000 claims abstract description 38
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims abstract description 38
- 235000019289 ammonium phosphates Nutrition 0.000 claims abstract description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 37
- 229910052742 iron Inorganic materials 0.000 claims abstract description 36
- 238000001354 calcination Methods 0.000 claims abstract description 33
- 229910000398 iron phosphate Inorganic materials 0.000 claims abstract description 33
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 33
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000001035 drying Methods 0.000 claims abstract description 32
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 32
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 32
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 32
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 32
- 239000002245 particle Substances 0.000 claims abstract description 32
- 238000001816 cooling Methods 0.000 claims abstract description 28
- CYKMNKXPYXUVPR-UHFFFAOYSA-N [C].[Ti] Chemical compound [C].[Ti] CYKMNKXPYXUVPR-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000005406 washing Methods 0.000 claims abstract description 26
- 239000002131 composite material Substances 0.000 claims abstract description 25
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 24
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 21
- 239000012066 reaction slurry Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 238000001694 spray drying Methods 0.000 claims abstract description 14
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 12
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 12
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 12
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 239000012047 saturated solution Substances 0.000 claims abstract description 8
- 238000012216 screening Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 60
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- 238000004321 preservation Methods 0.000 claims description 27
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 21
- 230000000630 rising effect Effects 0.000 claims description 21
- 239000011261 inert gas Substances 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- -1 ammonium phosphate compound Chemical class 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 239000003337 fertilizer Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000012452 mother liquor Substances 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- 239000007921 spray Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000005056 compaction Methods 0.000 abstract description 11
- 239000013078 crystal Substances 0.000 abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000007599 discharging Methods 0.000 description 6
- 239000000428 dust Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 206010003694 Atrophy Diseases 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 230000037444 atrophy Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 238000010902 jet-milling Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of high-energy-density lithium iron phosphate. Dissolving ammonium bicarbonate in water to prepare a saturated solution, cooling, keeping the temperature constant, adding a ferrous sulfate solution and an ammonium phosphate solution, adding an acid-base regulator and hydrogen peroxide to obtain a reaction slurry, filtering, washing, drying, adding an ethanol-butyl titanate solution into the dried material, stirring, slurrying uniformly, performing spray drying to obtain a dried material, calcining the dried material in a rotary furnace under nitrogen atmosphere to obtain the carbon-titanium composite anhydrous iron phosphate, uniformly mixing with a lithium source and a carbon source, grinding and drying, putting the obtained dried material into a roller furnace, calcining under the protection of inert atmosphere, cooling to obtain a calcined material, crushing the calcined material by airflow, and screening to remove iron to obtain the lithium iron phosphate. The invention can obtain the lithium iron phosphate material with high conductivity, low internal resistance and large single crystal particles, has excellent electrical property and high compaction density, thereby obtaining the lithium iron phosphate with high energy density.
Description
Technical Field
The invention relates to a preparation method of high-energy-density lithium iron phosphate, belonging to the technical field of lithium batteries.
Background
The total yield of 123 thousands of new energy automobiles in 2018 accounts for 60% of the total global sales, and the power battery installation 56Gwh is increased by 68% on a same scale. In 2018, under the background that the whole automobile city slides down, the new energy automobile still gives out a perfect answer sheet under the support of subsidies.
At present, the price of lithium iron phosphate of mainstream manufacturers is about 5.3 ten thousand yuan/ton, and compared with the price of 9-9.5 ten thousand yuan/ton in the last year, the price is reduced by over 61 percent. The price of the main stream of lithium iron phosphate falls to 5 ten thousand in the future, the price falls to bring about a great increase in demand, and the situation is different from the situation of market demand atrophy in the last year, the lithium iron phosphate shows a vigorous growth trend in the beginning of 2019, the installed electric quantity of the lithium iron phosphate battery is about 1.40GWH in 1 month in 2019, and the installed electric quantity is increased by 174% on a same scale.
As is known, the main bottleneck affecting the application of lithium iron phosphate is the low energy density, mainly due to the following reasons: the mainstream technology of the existing lithium iron phosphate is still carbon-coated lithium iron phosphate, but the technology has the following problems: the conductivity between particles of the carbon-coated lithium iron phosphate particles is increased, but the conductivity of a single particle of the lithium iron phosphate is not obviously improved; meanwhile, the carbon coated is flocculent amorphous carbon, and the carbon affects the compaction density of the lithium iron phosphate, because if the particles of the lithium iron phosphate are made to be larger, although the compaction density is high, the size of the particles is too large, the migration distance of lithium ions is far, the capacity is poor, and in order to ensure the capacity, the size of the particles can only be reduced, so that the compaction of the lithium iron phosphate is affected, and the capacity and the compaction are the same as those of a seesaw and cannot be achieved at the same time.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing lithium iron phosphate with high energy density, in which a carbon-titanium composite anhydrous iron phosphate is obtained, so as to obtain a lithium iron phosphate doped with carbon-titanium, and a sintering temperature can be increased in a manner of combining carbon-titanium doping with a coating carbon, so that a lithium iron phosphate material with high conductivity, low internal resistance and large single crystal particles can be obtained, and the lithium iron phosphate material with high energy density is obtained by excellent electrical properties and high compaction density.
The invention solves the technical problems by the following technical means:
the invention relates to a preparation method of high-energy-density lithium iron phosphate, which comprises the following steps:
1) dissolving ammonium bicarbonate in water, preparing a saturated solution at 45-55 ℃, then cooling to 20-25 ℃, keeping the temperature constant, simultaneously adding a ferrous sulfate solution and an ammonium phosphate solution, stirring and reacting for 15-30min after the addition, then adding an acid-base regulator and hydrogen peroxide, and reacting until the end-point pH is 2-2.5 to obtain a reaction slurry;
2) filtering and washing the reaction slurry, drying at the drying temperature of 110-;
3) and uniformly mixing the obtained carbon-titanium composite anhydrous iron phosphate, a lithium source and a carbon source, grinding and drying, putting the obtained dried material into a roller furnace, calcining under the protection of inert atmosphere, cooling to obtain a calcined material, and screening and deironing the calcined material after air flow crushing to obtain the lithium iron phosphate.
The cooling speed of the saturated ammonium hydrogen carbonate solution in the step (1) in the cooling process is 1.5-2 ℃/h, the concentrations of the ferrous sulfate solution and the ammonium phosphate solution are 1-1.5mol/L and 2-3mol/L respectively, the time for adding the ferrous sulfate solution and the ammonium phosphate solution is 30-60min, the volume of the added saturated ammonium hydrogen carbonate solution is 1/10-1/4 of the total volume of the ferrous sulfate solution and the ammonium phosphate solution, the concentrations of the acid-base regulator and the hydrogen peroxide are 7-10mol/L, the time for adding the acid-base regulator and the hydrogen peroxide is 30-60min, the temperature is raised to 90-95 ℃ after the acid-base regulator and the hydrogen peroxide are added, and the reaction slurry is obtained after the reaction at the temperature for 30-60 min.
The molar ratio of the ferrous sulfate, the ammonium phosphate, the acid-base regulator and the hydrogen peroxide added in the step (1) is 1: 1.01-1.02:0.5-3.05:0.6-0.65.
And (3) stopping washing until the conductivity of washing water is less than or equal to 200 mu S/cm in the step (2), mixing the mother liquor with the washing liquid, concentrating and crystallizing to obtain the ammonium phosphate compound fertilizer, drying until the moisture content of the material is less than 0.1%, stopping drying until the concentration of the butyl titanate in the ethanol-butyl titanate solution is 0.05-0.2mol/L, and the molar ratio of the added butyl titanate to the iron in the dried material is 0.5-1: 100.
And (3) adopting a centrifugal spray dryer in the spray drying process in the step (2), maintaining the linear speed of the atomizing wheel at 7000-.
And (3) in the calcining process of the dried material in the rotary furnace in the nitrogen atmosphere in the step (2), maintaining the nitrogen content in the gas in the rotary furnace to be more than 80 percent and the oxygen content to be 1-3 percent.
The molar ratio of the sum of the moles of iron and titanium in the carbon-titanium composite anhydrous iron phosphate to the moles of lithium in the lithium source in the step (3) is 1:1.02-1.05, and the mass ratio of carbon in the carbon-titanium composite anhydrous iron phosphate to carbon remained in the carbon source in the calcining process is 1: 0.5-1.
The calcination process in the step (3) is divided into a temperature rising section, a heat preservation section and a temperature reduction section, wherein the temperature rising speed is 200 ℃ per hour, the temperature rises to 820 ℃ with 790 ℃ with the addition of heat, the temperature enters the heat preservation section, the heat preservation time is 7-10 hours, the heat preservation temperature is 820 ℃ with the addition of heat, the temperature is reduced to less than or equal to 80 ℃, then the material is discharged, the inert gas is nitrogen, the volume of the inert gas introduced per minute is 150 times of the volume of the material entering the furnace per minute, the inert gas is pumped away by a draught fan in the temperature rising section and the temperature reduction section, and the pressure in the roller furnace is maintained to be higher than the external air pressure by 150Pa with the addition of heat.
And (3) after the calcined material is pulverized into particles with the particle size of 1.6-2.0 microns by air flow, sieving the particles by an ultrasonic vibration sieve with the mesh number of 60-80 meshes, removing iron by using a 2-level battery iron remover, and stopping removing iron until the magnetic substance is less than 0.5ppm to obtain the high-energy-density lithium iron phosphate.
The acid-base regulator is ammonia water or phosphoric acid.
Preparing saturated solution from ammonium bicarbonate at a higher temperature, cooling, crystallizing and separating out part of ammonium bicarbonate, keeping the temperature constant, adding a ferrous sulfate solution and an ammonium phosphate solution, generating iron precipitate under the reaction condition, taking the crystallized and separated ammonium bicarbonate as a crystal nucleus or mutually doping with the ammonium bicarbonate, simultaneously forming coprecipitation of carbonate and phosphate radicals and iron ions to form coated or doped iron salt precipitate, adding an acid-base regulator and hydrogen peroxide, reacting until the final pH is 2-2.5 to obtain reaction slurry, further improving the precipitation rate of the iron ions at the pH so that the precipitation rate of the iron is improved to over 98 percent, filtering, washing, drying at the drying temperature of 110-150 ℃, thermally decomposing the ammonium bicarbonate at the temperature to obtain carbon dioxide, Ammonia, water vapor, etc., and then form holes and hollow structures.
Adding the dried material into an ethanol-butyl titanate solution, stirring and slurrying uniformly, immersing the ethanol-butyl titanate solution into holes of iron phosphate, performing spray drying, volatilizing ethanol, precipitating residual butyl titanate, remaining the residual butyl titanate in the holes of the iron phosphate, volatilizing the solution on the surface of the iron phosphate, remaining the butyl titanate on the surface of the iron phosphate, distributing the butyl titanate on the holes and the surface of the iron phosphate, calcining the dried material in a rotary furnace under a nitrogen atmosphere at the calcining temperature of 500-600 ℃, calcining for 4-7h, combining oxygen in the butyl titanate with hydrogen to obtain water vapor, doping the residual carbon in the iron phosphate, forming a small amount of carbon on the surface of the iron phosphate, obtaining titanium dioxide from titanium in the butyl titanate and doping the titanium dioxide in the iron phosphate, obtaining the carbon-titanium composite anhydrous iron phosphate.
Uniformly mixing the carbon-titanium composite anhydrous iron phosphate, the lithium source and the carbon source, grinding and drying, putting the obtained dried material into a roller furnace, calcining under the protection of inert atmosphere, cooling to obtain a calcined material, carrying out jet milling on the calcined material, and screening to remove iron to obtain the lithium iron phosphate.
According to the lithium iron phosphate obtained by the invention, carbon exists in the lithium iron phosphate in two modes, including coated carbon and doped carbon, and most of titanium is doped in the lithium iron phosphate, so that the internal resistance of the lithium iron phosphate is reduced.
The sintering temperature of the conventional lithium iron phosphate is generally lower than 770 ℃, and the electrical property of the lithium iron phosphate is sharply reduced due to too high sintering temperature. But the sintering temperature of the invention can reach 790-820 ℃ without obviously reducing the electrical property of the lithium iron phosphate.
The invention has the beneficial effects that: the lithium iron phosphate material with high conductivity, low internal resistance and large single crystal particles can be obtained by combining the carbon-titanium-doped and coated carbon, and the lithium iron phosphate material with excellent electrical property and high compaction density can be obtained.
Drawings
FIG. 1 is an SEM of example 1 of the present invention.
Figure 2 is an XRD of example 1 of the invention.
FIG. 3 is an SEM of example 2 of the invention.
FIG. 4 is an SEM of example 3 of the invention.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific examples, wherein the method for preparing high energy density lithium iron phosphate of the present embodiment comprises the following steps:
1) dissolving ammonium bicarbonate in water, preparing a saturated solution at 45-55 ℃, then cooling to 20-25 ℃, keeping the temperature constant, simultaneously adding a ferrous sulfate solution and an ammonium phosphate solution, stirring and reacting for 15-30min after the addition, then adding an acid-base regulator and hydrogen peroxide, and reacting until the end-point pH is 2-2.5 to obtain a reaction slurry;
2) filtering and washing the reaction slurry, drying at the drying temperature of 110-;
3) and uniformly mixing the obtained carbon-titanium composite anhydrous iron phosphate, a lithium source and a carbon source, grinding and drying, putting the obtained dried material into a roller furnace, calcining under the protection of inert atmosphere, cooling to obtain a calcined material, and screening and deironing the calcined material after air flow crushing to obtain the lithium iron phosphate.
The cooling speed of the saturated ammonium hydrogen carbonate solution in the step (1) in the cooling process is 1.5-2 ℃/h, the concentrations of the ferrous sulfate solution and the ammonium phosphate solution are 1-1.5mol/L and 2-3mol/L respectively, the time for adding the ferrous sulfate solution and the ammonium phosphate solution is 30-60min, the volume of the added saturated ammonium hydrogen carbonate solution is 1/10-1/4 of the total volume of the ferrous sulfate solution and the ammonium phosphate solution, the concentrations of the acid-base regulator and the hydrogen peroxide are 7-10mol/L, the time for adding the acid-base regulator and the hydrogen peroxide is 30-60min, the temperature is raised to 90-95 ℃ after the acid-base regulator and the hydrogen peroxide are added, and the reaction slurry is obtained after the reaction at the temperature for 30-60 min.
The molar ratio of the ferrous sulfate, the ammonium phosphate, the acid-base regulator and the hydrogen peroxide added in the step (1) is 1: 1.01-1.02:0.5-3.05:0.6-0.65.
And (3) stopping washing until the conductivity of washing water is less than or equal to 200 mu S/cm in the step (2), mixing the mother liquor with the washing liquid, concentrating and crystallizing to obtain the ammonium phosphate compound fertilizer, drying until the moisture content of the material is less than 0.1%, stopping drying until the concentration of the butyl titanate in the ethanol-butyl titanate solution is 0.05-0.2mol/L, and the molar ratio of the added butyl titanate to the iron in the dried material is 0.5-1: 100.
And (3) adopting a centrifugal spray dryer in the spray drying process in the step (2), maintaining the linear speed of the atomizing wheel at 7000-.
And (3) in the calcining process of the dried material in the rotary furnace in the nitrogen atmosphere in the step (2), maintaining the nitrogen content in the gas in the rotary furnace to be more than 80 percent and the oxygen content to be 1-3 percent.
The molar ratio of the sum of the moles of iron and titanium in the carbon-titanium composite anhydrous iron phosphate to the moles of lithium in the lithium source in the step (3) is 1:1.02-1.05, and the mass ratio of carbon in the carbon-titanium composite anhydrous iron phosphate to carbon remained in the carbon source in the calcining process is 1: 0.5-1.
The calcination process in the step (3) is divided into a temperature rising section, a heat preservation section and a temperature reduction section, wherein the temperature rising speed is 200 ℃ per hour, the temperature rises to 820 ℃ with 790 ℃ with the addition of heat, the temperature enters the heat preservation section, the heat preservation time is 7-10 hours, the heat preservation temperature is 820 ℃ with the addition of heat, the temperature is reduced to less than or equal to 80 ℃, then the material is discharged, the inert gas is nitrogen, the volume of the inert gas introduced per minute is 150 times of the volume of the material entering the furnace per minute, the inert gas is pumped away by a draught fan in the temperature rising section and the temperature reduction section, and the pressure in the roller furnace is maintained to be higher than the external air pressure by 150Pa with the addition of heat.
And (3) after the calcined material is pulverized into particles with the particle size of 1.6-2.0 microns by air flow, sieving the particles by an ultrasonic vibration sieve with the mesh number of 60-80 meshes, removing iron by using a 2-level battery iron remover, and stopping removing iron until the magnetic substance is less than 0.5ppm to obtain the high-energy-density lithium iron phosphate.
The acid-base regulator is ammonia water or phosphoric acid.
Example 1
A preparation method of high-energy density lithium iron phosphate comprises the following steps:
1) dissolving ammonium bicarbonate in water, preparing a saturated solution at 50 ℃, then cooling to 20 ℃, keeping the temperature constant, simultaneously adding a ferrous sulfate solution and an ammonium phosphate solution, stirring and reacting for 15-30min after the addition, then adding an acid-base regulator and hydrogen peroxide, and reacting until the end point pH is 2.3 to obtain reaction slurry;
2) filtering and washing the reaction slurry, drying at 125 ℃, adding the dried material into an ethanol-butyl titanate solution, stirring and slurrying uniformly, and then carrying out spray drying to obtain a dried material, calcining the dried material in a rotary furnace under the nitrogen atmosphere at 550 ℃ for 6 hours to obtain the carbon-titanium composite anhydrous iron phosphate;
3) and uniformly mixing the obtained carbon-titanium composite anhydrous iron phosphate, a lithium source and a carbon source, grinding and drying, putting the obtained dried material into a roller furnace, calcining under the protection of inert atmosphere, cooling to obtain a calcined material, and screening and deironing the calcined material after air flow crushing to obtain the lithium iron phosphate.
The cooling speed of the saturated ammonium hydrogen carbonate solution in the step (1) in the cooling process is 1.8 ℃/h, the concentrations of the ferrous sulfate solution and the ammonium phosphate solution are 1.5mol/L and 3mol/L respectively, the time for adding the ferrous sulfate solution and the ammonium phosphate solution is 50min, the volume of the saturated ammonium hydrogen carbonate solution is 1/5 of the total volume of the ferrous sulfate solution and the ammonium phosphate solution, the concentrations of the acid-base regulator and the hydrogen peroxide are 8mol/L, the time for adding the acid-base regulator and the hydrogen peroxide is 50min, after the acid-base regulator and the hydrogen peroxide are added, the temperature is raised to 93 ℃, and the reaction slurry is obtained after the acid-base regulator and the hydrogen peroxide are added.
The molar ratio of the ferrous sulfate, the ammonium phosphate, the acid-base regulator and the hydrogen peroxide added in the step (1) is 1: 1.015:2.5:0.63.
And (3) stopping washing until the conductivity of washing water is less than or equal to 200 mu S/cm in the step (2), mixing the mother liquor with the washing liquid, concentrating and crystallizing to obtain the ammonium phosphate compound fertilizer, drying until the moisture content of the material is less than 0.1%, stopping drying until the concentration of the butyl titanate in the ethanol-butyl titanate solution is 0.1mol/L, and controlling the molar ratio of the added butyl titanate to the iron in the dried material to be 0.8: 100.
And (3) in the step (2), a centrifugal spray dryer is adopted in the spray drying process, the linear speed of an atomizing wheel is maintained at 8000m/s, hot nitrogen is adopted as a heat source in the spray drying process, the temperature of the hot nitrogen is 225 ℃, the discharging temperature is 80 ℃, meanwhile, gas after dust collection by a bag dust collector is condensed to recover alcohol and then discharged, and the recovered alcohol is returned to dissolve the butyl titanate.
And (3) in the calcining process of the dried material in the rotary furnace in the nitrogen atmosphere in the step (2), maintaining the nitrogen content in the gas in the rotary furnace to be more than 80 percent and the oxygen content to be 1.5 percent.
The molar ratio of the sum of the moles of iron and titanium in the carbon-titanium composite anhydrous iron phosphate to the moles of lithium in the lithium source in the step (3) is 1:1.035, and the mass ratio of carbon in the carbon-titanium composite anhydrous iron phosphate to carbon remaining in the carbon source in the calcining process is 1: 0.8.
And (3) the calcining process in the step (3) is divided into a temperature rising section, a heat preservation section and a temperature reduction section, the temperature rising speed in the temperature rising section process is 180 ℃/h, the temperature rises to 800 ℃, the temperature enters the heat preservation section, the heat preservation section process is carried out, the heat preservation time is 9h, the heat preservation temperature is 800 ℃, the temperature is reduced to the material temperature which is less than or equal to 80 ℃, then discharging is carried out, the inert gas is nitrogen, the volume of the inert gas introduced per minute is 135 times of the volume of the material entering the furnace per minute, the inert gas is pumped away by a draught fan in the temperature rising section and the temperature reduction section, and the pressure in the roller bed furnace is maintained to.
And (3) after the calcined material is pulverized into particles with the particle size of 1.8 microns by air flow, sieving the particles by an ultrasonic vibration sieve with the mesh number of 60 meshes, removing iron by using a 2-grade battery iron remover, and stopping removing iron until the magnetic substance is less than 0.5ppm to obtain the high-energy-density lithium iron phosphate.
The acid-base regulator is phosphoric acid.
Example 2
A preparation method of high-energy density lithium iron phosphate comprises the following steps:
1) dissolving ammonium bicarbonate in water, preparing a saturated solution at 50 ℃, then cooling to 20 ℃, keeping the temperature constant, simultaneously adding a ferrous sulfate solution and an ammonium phosphate solution, stirring and reacting for 20min after the addition, then adding an acid-base regulator and hydrogen peroxide, and reacting until the end point pH is 2.5 to obtain reaction slurry;
2) filtering and washing the reaction slurry, drying at 145 ℃, adding the dried material into an ethanol-butyl titanate solution, stirring and slurrying uniformly, and then carrying out spray drying to obtain a dried material, calcining the dried material in a rotary furnace under the nitrogen atmosphere at 580 ℃ for 7 hours to obtain the carbon-titanium composite anhydrous iron phosphate;
3) and uniformly mixing the obtained carbon-titanium composite anhydrous iron phosphate, a lithium source and a carbon source, grinding and drying, putting the obtained dried material into a roller furnace, calcining under the protection of inert atmosphere, cooling to obtain a calcined material, and screening and deironing the calcined material after air flow crushing to obtain the lithium iron phosphate.
The cooling speed of the saturated ammonium hydrogen carbonate solution in the step (1) in the cooling process is 2 ℃/h, the concentrations of the ferrous sulfate solution and the ammonium phosphate solution are 1.5mol/L and 3mol/L respectively, the time for adding the ferrous sulfate solution and the ammonium phosphate solution is 45min, the volume of the added saturated ammonium hydrogen carbonate solution is 1/4 of the total volume of the ferrous sulfate solution and the ammonium phosphate solution, the concentrations of the acid-base regulator and the hydrogen peroxide are 8mol/L, the time for adding the acid-base regulator and the hydrogen peroxide is 50min, after the acid-base regulator and the hydrogen peroxide are added, the temperature is raised to 92 ℃, and the reaction slurry is obtained after the temperature is raised for 50 min.
The molar ratio of the ferrous sulfate, the ammonium phosphate, the acid-base regulator and the hydrogen peroxide added in the step (1) is 1: 1.015:3.02:0.64.
And (3) stopping washing until the conductivity of washing water is less than or equal to 200 mu S/cm in the step (2), mixing the mother liquor with the washing liquid, concentrating and crystallizing to obtain the ammonium phosphate compound fertilizer, drying until the moisture content of the material is less than 0.1%, stopping drying until the concentration of the butyl titanate in the ethanol-butyl titanate solution is 0.12mol/L, and controlling the molar ratio of the added butyl titanate to the iron in the dried material to be 0.8: 100.
And (3) in the step (2), a centrifugal spray dryer is adopted in the spray drying process, the linear speed of an atomizing wheel is maintained at 8000m/s, hot nitrogen is adopted as a heat source in the spray drying process, the temperature of the hot nitrogen is 245 ℃, the discharging temperature is 80 ℃, meanwhile, gas after dust collection by a bag dust collector is condensed to recover alcohol and then discharged, and the recovered alcohol is returned to dissolve butyl titanate.
And (3) in the calcining process of the dried material in the rotary furnace in the nitrogen atmosphere in the step (2), maintaining the nitrogen content in the gas in the rotary furnace to be more than 80 percent and the oxygen content to be 2.5 percent.
The molar ratio of the sum of the moles of iron and titanium in the carbon-titanium composite anhydrous iron phosphate to the moles of lithium in the lithium source in the step (3) is 1:1.045, and the mass ratio of carbon in the carbon-titanium composite anhydrous iron phosphate to carbon remaining in the carbon source in the calcining process is 1: 0.9.
And (3) the calcining process in the step (3) is divided into a temperature rising section, a heat preservation section and a temperature reduction section, the temperature rising speed in the temperature rising section process is 150 ℃/h, the temperature rises to 810 ℃, then the temperature rises to enter the heat preservation section, the heat preservation time in the heat preservation section process is 8h, the heat preservation temperature is 810 ℃, then the temperature is reduced to the material temperature which is less than or equal to 80 ℃, then discharging is carried out, the inert gas is nitrogen, the volume of the inert gas introduced per minute is 140 times of the volume of the material entering the furnace per minute, the inert gas is pumped away by a draught fan in the temperature rising section and the temperature reduction section, and the pressure in the roller furnace is maintained to.
And (3) after the calcined material is pulverized into particles with the particle size of 1.8 microns by air flow, sieving the particles by an ultrasonic vibration sieve with the mesh number of 70 meshes, removing iron by using a 2-grade battery iron remover, and stopping removing iron until the magnetic substance is less than 0.5ppm to obtain the high-energy-density lithium iron phosphate.
The acid-base regulator is phosphoric acid.
Example 3
A preparation method of high-energy density lithium iron phosphate comprises the following steps:
1) dissolving ammonium bicarbonate in water, preparing a saturated solution at 50 ℃, then cooling to 20 ℃, keeping the temperature constant, simultaneously adding a ferrous sulfate solution and an ammonium phosphate solution, stirring and reacting for 20min after the addition, then adding an acid-base regulator and hydrogen peroxide, and reacting until the end point pH is 2.5 to obtain reaction slurry;
2) filtering and washing the reaction slurry, drying at 145 ℃, adding the dried material into an ethanol-butyl titanate solution, stirring and slurrying uniformly, and then carrying out spray drying to obtain a dried material, calcining the dried material in a rotary furnace under the nitrogen atmosphere at 580 ℃ for 7 hours to obtain the carbon-titanium composite anhydrous iron phosphate;
3) and uniformly mixing the obtained carbon-titanium composite anhydrous iron phosphate, a lithium source and a carbon source, grinding and drying, putting the obtained dried material into a roller furnace, calcining under the protection of inert atmosphere, cooling to obtain a calcined material, and screening and deironing the calcined material after air flow crushing to obtain the lithium iron phosphate.
The cooling speed of the saturated ammonium hydrogen carbonate solution in the step (1) in the cooling process is 2 ℃/h, the concentrations of the ferrous sulfate solution and the ammonium phosphate solution are 1.5mol/L and 3mol/L respectively, the time for adding the ferrous sulfate solution and the ammonium phosphate solution is 45min, the volume of the added saturated ammonium hydrogen carbonate solution is 1/4 of the total volume of the ferrous sulfate solution and the ammonium phosphate solution, the concentrations of the acid-base regulator and the hydrogen peroxide are 8mol/L, the time for adding the acid-base regulator and the hydrogen peroxide is 50min, after the acid-base regulator and the hydrogen peroxide are added, the temperature is raised to 92 ℃, and the reaction slurry is obtained after the temperature is raised for 50 min.
The molar ratio of the ferrous sulfate, the ammonium phosphate, the acid-base regulator and the hydrogen peroxide added in the step (1) is 1: 1.015:3.02:0.64.
And (3) stopping washing until the conductivity of washing water is less than or equal to 200 mu S/cm in the step (2), mixing the mother liquor with the washing liquid, concentrating and crystallizing to obtain the ammonium phosphate compound fertilizer, drying until the moisture content of the material is less than 0.1%, stopping drying until the concentration of the butyl titanate in the ethanol-butyl titanate solution is 0.12mol/L, and controlling the molar ratio of the added butyl titanate to the iron in the dried material to be 0.8: 100.
And (3) in the step (2), a centrifugal spray dryer is adopted in the spray drying process, the linear speed of an atomizing wheel is maintained at 8000m/s, hot nitrogen is adopted as a heat source in the spray drying process, the temperature of the hot nitrogen is 245 ℃, the discharging temperature is 80 ℃, meanwhile, gas after dust collection by a bag dust collector is condensed to recover alcohol and then discharged, and the recovered alcohol is returned to dissolve butyl titanate.
And (3) in the calcining process of the dried material in the rotary furnace in the nitrogen atmosphere in the step (2), maintaining the nitrogen content in the gas in the rotary furnace to be more than 80 percent and the oxygen content to be 2.5 percent.
The molar ratio of the sum of the moles of iron and titanium in the carbon-titanium composite anhydrous iron phosphate to the moles of lithium in the lithium source in the step (3) is 1:1.045, and the mass ratio of carbon in the carbon-titanium composite anhydrous iron phosphate to carbon remaining in the carbon source in the calcining process is 1: 0.85.
And (3) the calcining process in the step (3) is divided into a temperature rising section, a heat preservation section and a temperature reduction section, the temperature rising speed in the temperature rising section process is 150 ℃/h, the temperature rises to 820 ℃, then the temperature is in the heat preservation section, the heat preservation time in the heat preservation section process is 8h, the heat preservation temperature is 820 ℃, then the temperature is reduced to the material temperature which is less than or equal to 80 ℃, then discharging is carried out, the inert gas is nitrogen, the volume of the inert gas introduced per minute is 140 times of the volume of the material entering the furnace per minute, the inert gas is pumped away by a draught fan in the temperature rising section and the temperature reduction section, and the pressure in the roller furnace is maintained to be.
And (3) after the calcined material is pulverized into particles with the particle size of 1.8 microns by air flow, sieving the particles by an ultrasonic vibration sieve with the mesh number of 70 meshes, removing iron by using a 2-grade battery iron remover, and stopping removing iron until the magnetic substance is less than 0.5ppm to obtain the high-energy-density lithium iron phosphate.
The acid-base regulator is phosphoric acid.
The lithium iron phosphate materials of examples 1 to 3 were subjected to the physicochemical properties and the power-on test, and the results were as follows:
the electricity deduction test method comprises the following steps: SP: the mass ratio of PVDF is 90: 5: and 5, assembling to obtain a power-on test, wherein the cut-off voltage is 2.0V.
The method for measuring the compaction density comprises the steps of putting lithium iron phosphate powder into a die of powder compaction measuring equipment, pressing the powder under the pressure of 3 tons until the thickness of the powder is not changed any more, and dividing the powder by the volume to obtain powder compaction data.
The SEM and XRD of the lithium iron phosphate obtained in example 1 are shown in figures 1 and 2, the particles are spherical, the mean value of single crystal particles is 420nm, part of super-large particles exist, the size exceeds 3 mu m, and the lithium iron phosphate has high crystallinity and no impurity phase.
The SEM of the lithium iron phosphate obtained in example 2 is shown in fig. 3, and the SEM of the lithium iron phosphate obtained in example 3 is shown in fig. 4, which are similar to fig. 1, and both of them are in the form of particles with a large particle size, and can improve compaction, and are substantially spheroidal.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (10)
1. A preparation method of high-energy-density lithium iron phosphate is characterized by comprising the following steps:
1) dissolving ammonium bicarbonate in water, preparing a saturated solution at 45-55 ℃, then cooling to 20-25 ℃, keeping the temperature constant, simultaneously adding a ferrous sulfate solution and an ammonium phosphate solution, stirring and reacting for 15-30min after the addition, then adding an acid-base regulator and hydrogen peroxide, and reacting until the end-point pH is 2-2.5 to obtain a reaction slurry;
2) filtering and washing the reaction slurry, drying at the drying temperature of 110-;
3) and uniformly mixing the obtained carbon-titanium composite anhydrous iron phosphate, a lithium source and a carbon source, grinding and drying, putting the obtained dried material into a roller furnace, calcining under the protection of inert atmosphere, cooling to obtain a calcined material, and screening and deironing the calcined material after air flow crushing to obtain the lithium iron phosphate.
2. The method for preparing lithium iron phosphate with high energy density according to claim 1, wherein the method comprises the following steps: the cooling speed of the saturated ammonium hydrogen carbonate solution in the step (1) in the cooling process is 1.5-2 ℃/h, the concentrations of the ferrous sulfate solution and the ammonium phosphate solution are 1-1.5mol/L and 2-3mol/L respectively, the time for adding the ferrous sulfate solution and the ammonium phosphate solution is 30-60min, the volume of the added saturated ammonium hydrogen carbonate solution is 1/10-1/4 of the total volume of the ferrous sulfate solution and the ammonium phosphate solution, the concentrations of the acid-base regulator and the hydrogen peroxide are 7-10mol/L, the time for adding the acid-base regulator and the hydrogen peroxide is 30-60min, the temperature is raised to 90-95 ℃ after the acid-base regulator and the hydrogen peroxide are added, and the reaction slurry is obtained after the reaction at the temperature for 30-60 min.
3. The method for preparing lithium iron phosphate with high energy density according to claim 1, wherein the method comprises the following steps: the molar ratio of the ferrous sulfate, the ammonium phosphate, the acid-base regulator and the hydrogen peroxide added in the step (1) is 1: 1.01-1.02:0.5-3.05:0.6-0.65.
4. The method for preparing lithium iron phosphate with high energy density according to claim 1, wherein the method comprises the following steps: and (3) stopping washing until the conductivity of washing water is less than or equal to 200 mu S/cm in the step (2), mixing the mother liquor with the washing liquid, concentrating and crystallizing to obtain the ammonium phosphate compound fertilizer, drying until the moisture content of the material is less than 0.1%, stopping drying until the concentration of the butyl titanate in the ethanol-butyl titanate solution is 0.05-0.2mol/L, and the molar ratio of the added butyl titanate to the iron in the dried material is 0.5-1: 100.
5. The method for preparing lithium iron phosphate with high energy density according to claim 1, wherein the method comprises the following steps: and (3) adopting a centrifugal spray dryer in the spray drying process in the step (2), maintaining the linear speed of the atomizing wheel at 7000-.
6. The method for preparing lithium iron phosphate with high energy density according to claim 1, wherein the method comprises the following steps: and (3) in the calcining process of the dried material in the rotary furnace in the nitrogen atmosphere in the step (2), maintaining the nitrogen content in the gas in the rotary furnace to be more than 80 percent and the oxygen content to be 1-3 percent.
7. The method for preparing lithium iron phosphate with high energy density according to claim 1, wherein the method comprises the following steps: the molar ratio of the sum of the moles of iron and titanium in the carbon-titanium composite anhydrous iron phosphate to the moles of lithium in the lithium source in the step (3) is 1:1.02-1.05, and the mass ratio of carbon in the carbon-titanium composite anhydrous iron phosphate to carbon remained in the carbon source in the calcining process is 1: 0.5-1.
8. The method for preparing lithium iron phosphate with high energy density according to claim 1, wherein the method comprises the following steps: the calcination process in the step (3) is divided into a temperature rising section, a heat preservation section and a temperature reduction section, wherein the temperature rising speed is 200 ℃ per hour, the temperature rises to 820 ℃ with 790 ℃ with the addition of heat, the temperature enters the heat preservation section, the heat preservation time is 7-10 hours, the heat preservation temperature is 820 ℃ with the addition of heat, the temperature is reduced to less than or equal to 80 ℃, then the material is discharged, the inert gas is nitrogen, the volume of the inert gas introduced per minute is 150 times of the volume of the material entering the furnace per minute, the inert gas is pumped away by a draught fan in the temperature rising section and the temperature reduction section, and the pressure in the roller furnace is maintained to be higher than the external air pressure by 150Pa with the addition of heat.
9. The method for preparing lithium iron phosphate with high energy density according to claim 1, wherein the method comprises the following steps: and (3) after the calcined material is pulverized into particles with the particle size of 1.6-2.0 microns by air flow, sieving the particles by an ultrasonic vibration sieve with the mesh number of 60-80 meshes, removing iron by using a 2-level battery iron remover, and stopping removing iron until the magnetic substance is less than 0.5ppm to obtain the high-energy-density lithium iron phosphate.
10. The method for preparing lithium iron phosphate with high energy density according to claim 1, wherein the method comprises the following steps: the acid-base regulator is ammonia water or phosphoric acid.
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